EP0994691B1 - Use of ester quaternaries as emulsifiers in preparations for coloring keratin fibers - Google Patents

Abstract

There is disclosed the use of esterquats (ie quaternised fatty acid esters of alkanolamines, e.g. ethanolamines and 2,3-dihydroxypropylamines, and especially triethanolamines) as emulsifiers for hair dyes for the production of formulations for colouring keratin fibres. Improved dye absorption by the hair is achieved and, at the same time, improved softness is imparted to the hair during colouring, when esterquats are included in the hair colouring formulation. Suitable esterquats are those of formulae (I),(II) and (III) as defined in claims 2,3 and 4 respectively.

Description

Field of the Invention

The invention relates to the use of esterquats as an emulsifier for hair dyes in Preparations for coloring keratin fibers.

State of the art

Synthetic-based hair dyes can be divided into three groups: the direct ones temporary, semi-permanent and permanent dyes. An assignment of natural Hair dye to one of the three groups is not, however, easily possible. Whether with individual Dyes a temporary, semi-permanent or permanent hair coloring can be achieved depends, among other things. also on the formulation in which they are incorporated or on how these formulations be applied.

The coloring that can be achieved with temporary, direct hair dyes is only a temporary one Change the existing hair color. It must therefore be easily washed out with shampoos his. It is due to the simple deposition of the dyes on the surface of the hair achieved; this coloring must therefore not be followed by a rinsing process. The dyes used must therefore have the following properties: weak affinity for hair keratin, easy to wash out through a shampoo, sufficient lightfastness and good abrasion resistance, so as not to wear clothes and Soiling pillows. For this purpose, azo, triphenylmethane, anthraquinone or indamine dyes and their leuco derivatives.

The semi-permanent hair dye gives the hair more pronounced and lasting shades, that last up to 5 or 6 washes. This is achieved through the use of dyes have a high affinity for keratin and penetrate relatively deeply into the interior of the hair fibers. The These colorants are used in many different ways: for example, adding reflexes to a natural color, gray ones Covering hair or removing gray or white hair from the yellow cast. The for this purpose suitable direct dyes are largely non-ionic or cationic in nature and have a low relative molecular weight and low water solubility. The important representatives are Nitrophenyldiamines, from which numerous other hair dyes result from substitution reactions have it made. The nitro dyes also include the nitroaminophenols, which - depending on the position their nitro and amino groups on the phenol ring - enable colorations that range from yellow to orange Go red. Azo or quinonimine dyes with quaternary ammonium groups have a high Affinity for hair keratin. Although they dye less intensely than the nitro dyes, they do allow Colorings in all shades.

The permanent hair coloring is ultimately very resistant to shampooing, exposure to light and other hair treatment methods. Here the dyes are directly on and in the hair formed by chemical reactions to which the uncolored intermediates or Intermediate products are subjected. Oxidation reactions and coupling processes or Condensation from hydrogen peroxide in the presence of ammonia or monoethanolamine are caused. The use of hydrogen peroxide as an oxidizing agent is preferred because it not only initiates the color formation, but also the melamine pigments of the hair destroyed and in this way causes bleaching. In addition to the real oxidation hair dyes the person skilled in the art also knows the self-oxidizing dyes which are already oxidized by atmospheric oxygen become. The nature of the oxidation dyes is in the oxidation bases (developer) and in the shaders (couplers) divided. Oxidation bases are aromatic compounds with at least two electron-donating groups, preferably amino and / or hydroxyl groups, are core-substituted and therefore easily oxidizable. The isomers are important representatives of these bases ortho- or para-phenyldiamines, aminophenols and dihydroxybenzenes. The couplers are are usually also aromatic compounds with amino and / or hydroxyl groups however, are in the meta position.

The hair colors can be applied to the hair in various forms. It can happen in the simplest case are aqueous or aqueous-alcoholic lotions that are currently in use Application diluted and applied to the hair. Another form of offerings are Spa lotions that, in addition to the dyes, also contain cation polymers, and therefore additionally cause a care effect. The same applies to foam aerosols. A typical form of offer for the semi-permanent coloring are tinted shampoos, while permanent hair colors usually can be applied as creams or gels. Problems particularly in the manufacture of shampoo formulations as well as creams and gels, on the one hand, consist of the dye together with stable additives to emulsify stably and on the other hand the rapid deposition on the Ensure keratin fibers.

In this connection, a method for dyeing cotton is known from Russian patent application SU 956.668 , in which ester quats based on tall oil fatty acid are used. Patent application GB 2 168 082 A2 discloses a hair colorant in which the color intensity on the hair is increased with cationic surfactants. A process for the production of solid ester quats with improved emulsifying power, which are used for the production in cosmetic compositions , is described in the international patent application WO 94 21592 A.

The complex object of the present invention was thus emulsifiers for hair dyes to make available, with the help of which emulsions can be produced, which also prolonged storage or under the influence of heat neither separate nor change their viscosity. The one with it Preparations available should also lead to improved color absorption on the hair and maintain it at the same time, i.e. especially grip and gloss as well as combability improve.

Description of the invention

The invention relates to the use of esterquats as an emulsifier for hair dyes in Preparations for coloring keratin fibers.

Surprisingly, it has been found that esterquats are not only able to dye hair to emulsify permanently without the preparations changing their viscosity with the use of these Cationic surfactants as emulsifiers is also an easier absorption of the dye by the Keratin fibers connected. Another advantage is that during the dyeing the hair pleasant soft feel and shine and the static charge between the fibers is reduced becomes. In this sense, the use according to the invention is not only the desired one Coloring, but also achieved a care effect.

esterquats

The term "ester quats" generally means quaternized fatty acid triethanolamine ester salts. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this connection, reference is made to international patent application WO 91/01295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. Overviews on this topic have been published, for example, by R.Puchta et al. in tens. Surf. Det., 30 , 186 (1993), M.Brock in Tens. Surf. Det. 30 , 394 (1993), R. Lagerman et al. in J. Am. Oil. Chem. Soc., 71 , 97 (1994) and I. Shapiro in Cosm.Toil. 109 , 77 (1994) appeared.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quatemierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quatemierte Fettsäuretriethanolaminestersalze der Formel (I) als besonders vorteilhaft erwiesen, in der R¹CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R² für R¹CO, R³ für Wasserstoff, R⁴ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht.The quaternized fatty acid triethanolamine ester salts follow the formula (I)

in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, when natural fats and oils are split. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids as well as high elaidic acid C _16/18 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 - tallow or palm fatty acid (iodine number 0 to 40). From a technical point of view, quaternized fatty acid triethanolamine ester salts of the formula (I) have proven particularly advantageous in which R ¹ CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m , n and p is 0 and X is methyl sulfate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (III) should be mentioned as a further group of suitable ester quats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the examples given for (I) also apply to the esterquats of the formulas (II) and (III) . The esterquats usually come on the market in the form of 50 to 90% strength by weight alcoholic solutions, which can be diluted with water if required. However, it is also possible to use mixtures of esterquats with fatty alcohols, which are commercially available in the form of flakes and whose preparation is described in German patent DE-C1 4308794 (Henkel). The esterquats can be used in amounts of 0.1 to 5% by weight, preferably 1 to 3% by weight, based on the preparations.

hair dyes

For the purposes of the use according to the invention, suitable dyes are , for example, direct dyes , for example from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as those with the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57 , Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, picramic acid and Rodol 9 R known compounds and 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, (N-2,3-dihydroxypropyl-2-nitro -4-trifluoromethyl) amino-benzene and 4-N-ethyl-1,4-bis (2'hydroxyethylamino-no) -2-nitrobenzene hydrochloride. Natural dyes such as henna red, neutral henna, black henna, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root are also used.

In addition to the direct draws, oxidation dyes consisting of developer and coupler components can also be used. Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are used as developer components, for example. Special representatives include p-toluenediamine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido 4-amino-pyrazolone-5 and 4-amino-3-methylphenol, 2- (2-hydroxyethyl) -1,4-aminobenzene and 2,4,5,6-tetraaminopyrimidine. M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and pyridine derivatives are generally used as coupler components. Suitable coupler substances are in particular 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl -3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol , 2-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine and 2,6-diaminopyridine.

With regard to other dye components, the Colipa list, published by Industry Association for Personal Care and Detergents, Frankfurt. The hair dyes can in quantities of 0.001 to 1, preferably 0.3 to 0.7% by weight - calculated on the preparations - be used.

Other auxiliaries and additives

In a particularly simple embodiment of the invention, the preparations contain for coloring of keratin fibers in addition to the hair dyes, the esterquat emulsifiers and water only 01 body. However, it is also possible to prepare, for example, tinting or coloring shampoos to offer, which then also other ingredients typical of the type of preparations such as for example mild surfactants, co-emulsifiers, superfatting agents, pearlescent waxes, stabilizers, Consistency enhancers, thickeners, cation polymers, silicone compounds, biogenic agents, antidandruff agents, Film formers, preservatives, hydrotropes, solubilizers, UV light protection filters, Perfume oils, dyes and the like can contain.

Typical examples of suitable mild, ie particularly skin-compatible surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid taurides, fatty acid glutamates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C ₁₃ carboxylic acids are, for example, oil bodies with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids , in particular benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (eg Finsolv® TN), dialkyl ethers, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons. The amount of oil bodies in the preparations is typically 10 to 70, preferably 25 to 50% by weight.

(1) Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;

(2) C_12/18-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;

(3) Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;

(4) Alkylmono- und -oligoglycoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analoga;

(5) Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;

(6) Polyol- und insbesondere Polyglycerinester wie z.B. Polyglycerinpolyricinoleat oder Polyglycerinpoly-12-hydroxystearat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen;

(7) Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;

(8) Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C_6/22-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipentaerythrit, Zuckeralkohole (z.B. Sorbit), Alkylglucoside (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucoside (z.B. Cellulose);

(9) Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate;

(10) Wollwachsalkohole;

(11) Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;

(12) Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE-PS 1165574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin sowie

(13) Polyalkylenglycole.

Examples of suitable co-emulsifiers are nonionic surfactants from at least one of the following groups:

(1) Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group;

(2) C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;

(3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;

(5) adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

(6) polyol and especially polyglycerol esters such as polyglycerol polyricinoleate or polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes of substances are also suitable;

(7) adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

(8) _{partial esters} based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucoside (e.g. methyl glucoside), butyl glucoside as well as polyglucosides (eg cellulose);

(9) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;

(10) wool wax alcohols;

(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol and

(13) Polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which Degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations.

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use as surface-active substances are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. With regard to the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylimide-3-carboxylimethyl-3-carboxylimethyl-3-carboxylimethyl-3-carboxylimethyl-3-carboxylimethyl-3-carboxylimethyl-3-carboxylimethyl-3-carboxylimethyl-3-carboxylimide each with 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acyl aminoethyl aminopropionate and C _12/18 acyl sarcosine.

Substances such as, for example, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.

Pearlescent waxes that can be used are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups; as well as their mixtures.

The consistency factors mainly used are fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred. Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and di-esters of fatty acids, polyacrylates (e.g. Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides, and electrolytes such as sodium chloride and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as, for example, Luviquat® (BASF ), Condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as amidomethicones, copolymers of adipic acid and dimethylaminetetrynoxydiamine / copolymers of acrylate (D) arylalohydroxy (d) arylalohydroxy (d) aryl-hydroxy-dehydro-vinyl-aminohydroxypropyldiamine-dicarene-hydroxy-dehydro-hydroxymethyl-aminohydroxy-dmethyl-hydroxy-dehydro-hydroxypropyl-dehydro-aminoxydiamine-dicarboxylic acid (C) with dimethyidiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides as described for example in FR-A 2252840 and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan otherwise microcrystalline, condensation products from dihaloalkylene such as dibromobutane with bisdialkylamines such as bis-dimethylamino-1,3-propane, cationic guar gum such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt Polymers such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine- and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature. Typical examples of fats are glycerides while suitable waxes inter alia, beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax or microcrystalline waxes, optionally in combination with hydrophilic waxes, for example cetyl stearyl alcohol or partial glycerides. Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate can be used as stabilizers . Biogenic active substances are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes. As anti-dandruff agents Climbazol, Octopirox® and zinc pyrithione. Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinyl-pyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds. Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases.

UV light protection filters are understood to mean organic substances which are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, for example heat. Typical examples are 4-aminobenzoic acid and its esters and derivatives (e.g. 2-ethylhexyl-p-dimethylaminobenzoate or p-dimethylaminobenzoic acid octyl ester), methoxycinnamic acid and its derivatives (e.g. 4-methoxycinnamic acid-2-ethylhexyl ester), benzophenones (e.g. oxybenzone, 2-hydroxy- 4-methoxybenzophenone), dibenzoylmethane, salicylate ester, 2-phenylbenzimidazole-5-sulfonic acid, 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 3- (4'- Methyl) benzylidenbornan-2-one, methylbenzylidene camphor and the like. Finely dispersed metal oxides or salts are also suitable for this purpose, such as, for example, titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc) and barium sulfate. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or shape which differs from the spherical shape in some other way. In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples are superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).

• Glycerin;
• Alkylenglycole wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;
• technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
• Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;
• Niedrigalkylglucoside, insbesondere solche, mit 1 bis 8 Kohlenstoffen im Alkylrest wie beispielsweise Methyl- und Butylglucosid;
• Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen wie beispielsweise Sorbit oder Mannit,
• Zucker mit 5 bis 12 Kohlenstoffatomen wie beispielsweise Glucose oder Saccharose;
• Aminozucker wie beispielsweise Glucamin.

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are

• glycerol;
• Alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
• technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;
• Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,
• Sugar with 5 to 12 carbon atoms such as glucose or sucrose;
• Aminosugars such as glucamine.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.

Perfume oils include extracts from flowers (lavender, roses, jasmine, neroli), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway seeds, juniper), fruit peels (bergamot, lemon, oranges), roots (Macis, Angelica, Celery, Cardamom, Costus, Iris, Calmus), woods (sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and branches (spruce, fir , Pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials such as musk, civet and castoreum are also suitable. Ambroxan, eugenol, isoeugenol, citronellal, hydroxycitronellal, geraniol, citronellol, geranyl acetate, citral, ionone and methylionone are suitable as synthetic or semi-synthetic perfume oils.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight on the middle - amount. The agents can be produced by customary cold or hot processes respectively; the phase inversion temperature method is preferably used.

Examples

Example 1. An emulsion was prepared by mixing at 70 ° C., comprising 33.3 g of Dehyquart® AU-46 (methyl-quaternized dipalm fatty acid triethanolamine ester, methyl sulfate salt, Pulcra SA, Barcelona), 9 g of C _8/18 alkyl glucoside, 9 g of colloidal silica, 3 g ammonium chloride, aqueous ammonia solution ad 100 g (pH = 10.5). 7.5 mmol each of a developer component (N, N'-bis (4-aminophenyl) piperidine) and a coupler component (resorcinol) were stirred into the emulsion at 20 ° C. The oxidative development was then carried out using hydrogen peroxide. The shade of the dyed hair was dark blonde.

Example 2. An emulsion was prepared analogously to Example 1, containing 33.3 g of Dehyquart® AU-46, 9 g of C _8/18 alkyl glucoside, 9 g of colloidal silica, 3 g of ammonium chloride, and aqueous ammonia solution to 100 g (pH = 10. 5). 7.5 mmol of 2,4,5,6-tetraaminopyridine and 2,6-bis (2-hydroxyethylamino) toluene were stirred into the PIT emulsion at 20 ° C. The oxidative development was again carried out with hydrogen peroxide. The shade of the dyed hair was deep red.

Examples 3 to 15. On the basis of these examples, the following hair dye cream emulsion was then produced cold (water ad 100% by weight): Cream base according to Example 1 or 2 50.0% by weight developer component 7.5 mmol Kupplerkomponente 7.5 mmol Na ₂ SO ₃ (inhibitor) 1.0% by weight (NH ₄ ) ₂ SO ₄ 1.0% by weight conc. ammonia solution ad pH 10

The ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to 10 using concentrated ammonia solution, and the mixture was then made up to 100 g with water. The oxidative development of the color was carried out using hydrogen peroxide solution as the oxidation solution. For this purpose, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (1, 3 or 9%) and mixed. The coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray, but not specially pretreated human hair and left there at 32 ° C for 30 minutes. After the dyeing process was completed, the hair was rinsed, washed with a conventional shampoo and then dried. Colorings according to Table 1 were found:

Claims (9)

1. The use of esterquats as emulsifiers for hair dyes in preparations for coloring keratin fibers.
2. The use claimed in claim 1, characterized in that esterquats corresponding to formula (I):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms R² and R³ independently of one another represent hydrogen or have the same meaning as R¹CO, R⁴ is an alkyl group containing 1 to 4 carbon atoms or a (CH₂CH₂O)_qH group, m, n and p together stand for 0 or numbers of 1 to 12, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate, are used.
3. The use claimed in claim 1, characterized in that esterquats corresponding to formula (II):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² is hydrogen or has the same meaning as R¹CO, R⁴ and R⁵ independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, are used.
4. The use claimed in claim 1, characterized in that esterquats corresponding to formula (III):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² is hydrogen or has the same meaning as R¹CO, R⁴, R⁶ and R⁷ independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, are used.
5. The use claimed in claims 1 to 4, characterized in that the esterquats are used in quantities of 0.1 to 5% by weight, based on the preparations.
6. The use claimed in claims 1 to 5, characterized in that substantive hair dyes or oxidation hair dyes are used.
7. The use claimed in claims 1 to 6, characterized in that the hair dyes are used in quantities of 0.001 to 1% by weight, based on the preparation.
8. The use claimed in claims 1 to 7, characterized in that oil components selected from the group consisting of Guerbet alcohols based on fatty alcohols containing 6 to 18 carbon atoms, esters of linear C_6-22 fatty acids with linear C_6-22 fatty alcohols, esters of branched C_6-13 carboxylic acids with linear C_6-22 fatty alcohols, esters of linear C_6-22 fatty acids with branched alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols and/or Guerbet alcohols, triglycerides based on C_6-10 fatty acids, liquid mono-/di-/triglyceride mixtures based on C_6-18 fatty acids, esters of C_6-22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C_6-22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched C_6-22 alcohols, dialkyl ethers, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons are additionally used.
9. The use claimed in claim 7, characterized in that the oils are used in quantities of 10 to 70% by weight, based on the preparations.